Surface Buckling and Subsurface Oxygen: Atomistic Insights into the Surface Oxidation of Pt(111)

Fantauzzi, Donato; Mueller, Jonathan E.; Sabo, Lehel; Duin, Adri C. T. van; Jacob, Timo

doi:10.1002/cphc.201500527

Cited by 55 publications

(65 citation statements)

References 26 publications

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“…5 for clarification). This finding is in agreement with the results presented in [32]. The reaction energies corresponding to Fig.…”

Section: Resultssupporting

confidence: 93%

“…A recent kinetic model of Rinaldo et al provides a comprehensive picture of surface electrochemical processes during oxide formation and reduction at Pt(111) in the voltage range of 0.65-1.15 V RHE [31]. Density functional theory (DFT), molecular dynamics (MD), and ab initio MD have also been employed to study involved reaction mechanisms at atomistic scales [32][33][34][35][36][37].…”

Section: Introductionmentioning

confidence: 99%

“…Fantauzzi et al [32] have performed reactive force field (ReaxFF) MD calculations to determine the surface energies for structures with up to one monolayer of oxygen on Pt(111). Their results reveal four stable surface phases corresponding to pure adsorbate, low-coverage and high-coverage buckled, and subsurface-oxygen structures, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…Their results reveal four stable surface phases corresponding to pure adsorbate, low-coverage and high-coverage buckled, and subsurface-oxygen structures, respectively. They have found that stable phases of Pt(111) with oxygen coverage beyond 0.56 ML contain subsurface oxygen [32]. The work of Gu and Balbuena [36] suggests that the tetra-I site is the energetically preferred site for adsorption of atomic oxygen in the subsurface of Pt(111).…”

Section: Introductionmentioning

confidence: 99%

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Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

Eslamibidgoli

Eikerling

2016

Electrocatalysis

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In this article, we propose a novel mechanism for the atomic-level processes that lead to oxide formation and eventually Pt dissolution at an oxidized Pt(111) surface. The mechanism involves a Pt extraction step followed by the substitution of chemisorbed oxygen to the subsurface. The energy diagrams of these processes have been generated using density functional theory and were analyzed to determine the critical coverages of chemisorbed oxygen for the Pt extraction and O ads substitution steps. The Pt extraction process depends on two essential conditions: (1) the local coordination of a Pt surface atom by three chemisorbed oxygen atoms at nearestneighboring fcc adsorption sites; (2) the interaction of the buckled Pt atom with surface water molecules. Results are discussed in terms of surface charging effects caused by oxygen coverage, surface strain effects, as well the contribution from electronic interaction effects. The utility of the proposed mechanism for the understanding of Pt stability at bimetallic surfaces will be demonstrated by evaluating the energy diagram of a Cu ML /Pt(111) near-surface alloy.

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“…5 for clarification). This finding is in agreement with the results presented in [32]. The reaction energies corresponding to Fig.…”

Section: Resultssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

Eslamibidgoli

Eikerling

2016

Electrocatalysis

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“…[6] Theinitial stages of surface oxidation are attributed to surface buckling and subsurface oxygen, resulting from processes that are both accessible at low temperatures. [5] Similar behavior has been observed in the presence of H 2 O. [7] At V O !…”

supporting

confidence: 74%

Growth of Stable Surface Oxides on Pt(111) at Near‐Ambient Pressures

et al. 2017

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Detailed knowledge of the structure and degree of oxidation of platinum surfaces under operando conditions is essential for understanding catalytic performance. However, experimental investigations of platinum surface oxides have been hampered by technical limitations, preventing in situ investigations at relevant pressures. As a result, the time-dependent evolution of oxide formation has only received superficial treatment. In addition, the amorphous structures of many surface oxides have hindered realistic theoretical studies. Using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) we show that a time scale of hours (t≥4 h) is required for the formation of platinum surface oxides. These experimental observations are consistent with ReaxFF grand canonical Monte Carlo (ReaxFF-GCMC) calculations, predicting the structures and coverages of stable, amorphous surface oxides at temperatures between 430-680 K and an O partial pressure of 1 mbar.

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Oxygen Diffusion in Platinum Electrodes: A Molecular Dynamics Study of the Role of Extended Defects

Zurhelle

Stehling

Waser

et al. 2021

Adv Materials Inter

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Platinum serves as a model electrode in solid‐state electrochemistry and as the inert electrode in redox‐based resistive random‐access memory (ReRAM) technology. Experimental work has proposed that oxygen may diffuse faster along platinum's extended defects, but quantitative, unambiguous transport data do not exist. In this study, the diffusion of oxygen atoms in crystalline platinum and along its extended defects is studied as a function of temperature by means of molecular dynamics (MD) simulations with the ReaxFF interatomic potentials. The MD simulations indicate that platinum vacancies trap oxygen atoms, inhibiting their diffusion through the platinum lattice and leading to a high activation enthalpy of diffusion of around 3 eV. This picture of trapping is supported by static density‐functional‐theory calculations. MD simulations of selected dislocations and selected grain boundaries indicate that oxygen diffusion is much faster along these extended defects than through the Pt lattice at temperatures below 1400 K, exhibiting a much lower activation enthalpy of ≈0.7 eV for all extended defects examined. Producing specific electrode microstructures with controlled densities and types of extended defects thus offers a new avenue to improve the performance of ReRAM devices and to prevent device failure.

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Surface Buckling and Subsurface Oxygen: Atomistic Insights into the Surface Oxidation of Pt(111)

Cited by 55 publications

References 26 publications

Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

Growth of Stable Surface Oxides on Pt(111) at Near‐Ambient Pressures

Oxygen Diffusion in Platinum Electrodes: A Molecular Dynamics Study of the Role of Extended Defects

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